WO2013062415A1 - Procédé de production de syngaz pour la production de méthanol - Google Patents

Procédé de production de syngaz pour la production de méthanol Download PDF

Info

Publication number
WO2013062415A1
WO2013062415A1 PCT/NL2012/050748 NL2012050748W WO2013062415A1 WO 2013062415 A1 WO2013062415 A1 WO 2013062415A1 NL 2012050748 W NL2012050748 W NL 2012050748W WO 2013062415 A1 WO2013062415 A1 WO 2013062415A1
Authority
WO
WIPO (PCT)
Prior art keywords
methanol
feed
synthesis gas
hydrocarbon
reforming
Prior art date
Application number
PCT/NL2012/050748
Other languages
English (en)
Inventor
Gaetano Iaquaniello
Elena ANTONETTI
Palma CONTALDO
Original Assignee
Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center filed Critical Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center
Priority to CN201280053004.5A priority Critical patent/CN103889891B/zh
Priority to DK12783359.8T priority patent/DK2771275T3/da
Priority to EP12783359.8A priority patent/EP2771275B1/fr
Priority to EA201400498A priority patent/EA026825B1/ru
Priority to US14/354,536 priority patent/US9102532B2/en
Priority to CA2853421A priority patent/CA2853421C/fr
Publication of WO2013062415A1 publication Critical patent/WO2013062415A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/28—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using moving solid particles
    • C01B3/30—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using moving solid particles using the fluidised bed technique
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series

Definitions

  • the present invention relates to the field of synthesis gas production from light hydrocarbons such as natural gas.
  • the present invention relates to the production of synthesis gas particularly suitable for methanol production.
  • methanol plants produce methanol in several steps, usually including synthesis gas preparation (reforming), methanol synthesis and methanol purification. Since these steps are conducted in separate process sections, the technology for each section can be selected and optimised independently. The usual criteria for the selection of technology are capital cost and plant efficiency. The preparation of synthesis gas and compression typically accounts for about 60% of the investment, and almost all energy is consumed in this process section. Therefore, the technology to produce synthesis gas is of major importance, regardless of the site.
  • the synthesis gas for the production of methanol is usually obtained by subjecting a desulfurized hydrocarbon feed to steam reforming (SR) at a temperature from 800 to 950°C in the presence of a fixed bed of catalyst, typically containing nickel.
  • SR steam reforming
  • the resulting synthesis gas is cooled and compressed to be used further in the methanol process.
  • the synthesis gas obtained in steam reforming is usually characterized by a too low carbon/hydrogen ratio compared to a stoichiometric composition optimal for methanol synthesis.
  • the methanol synthesis reactor typically operates at a large hydrogen excess which results in an overall low plant efficiency.
  • a combination of technologies can be used.
  • a known method for methanol production also known as Combined Reforming Technology (CRT) is described in EP 0233076.
  • CRT Combined Reforming Technology
  • a hydrocarbon feed is split into two feedstock fractions, of which one fraction is subjected to a primary steam reforming and is then combined with the second feedstock fraction.
  • the resulting mixture is reacted with an oxygen containing gas in a secondary reforming reactor.
  • the resulting raw synthesis gas is mixed with a hydrogen-rich stream obtained from the purge gas from a methanol synthesis loop, which final mixture is then fed to the synthesis loop for methanol production.
  • up to 50-60% of the entire feed needs to be subjected to steam reforming. This makes the steam
  • the invention presents, in one aspect, a method for producing synthesis gas from a hydrocarbon containing feed, comprising the steps of:
  • the invention in another aspect, is a method for producing methanol from a hydrocarbon containing feed comprising the steps according to claim 1 to obtain a synthesis gas, and using said synthesis gas to produce methanol.
  • the invention provides a method for adapting an existing methanol plant comprising a steam reforming unit to the methanol production process according to the invention, said method comprising adding a CPO unit in parallel with the steam reforming unit, to the existing methanol plant.
  • Figure 1 shows a block scheme of a conventional combined reformer with a pre-reforming section.
  • Figure 2 shows a block scheme for the production of synthesis gas according to an embodiment of the present invention, with a pre-reforming section only for a SR feed.
  • FIG. 3 shows a block scheme of an embodiment of the present invention with a common pre-reforming section. Detailed description of the invention
  • a hydrocarbon containing feed is divided into two feeds that are treated separately.
  • the resulting feeds are further recombined to obtain synthesis gas particularly suitable for methanol production.
  • a synthesis gas suitable for methanol production means that the synthesis gas has a certain ratio of components, especially of hydrogen and carbon oxides, which is optimal for methanol synthesis.
  • methanol synthesis gas can be
  • R ratio characterised by a molar ratio (3 ⁇ 4 - CO2) / (CO + CO2), referred to herein as an R ratio.
  • An R ratio equal to 2 defines a stoichiometric synthesis gas for formation of methanol.
  • the synthesis gas obtained according to the method of the present invention has preferably, an R ratio in the range of 1.90-2.20, more preferably 1.95-2.05.
  • CO to CO2 ratio important properties of the synthesis gas are the CO to CO2 ratio and the concentration of inerts.
  • a high CO to CO2 ratio will increase the reaction rate and conversion and also decrease the water formation, which in turn reduces the catalyst deactivation rate.
  • a high concentration of inerts will lower the partial pressure of the active reactants.
  • Inerts in the methanol synthesis are typically methane, argon and nitrogen.
  • a hydrocarbon containing feed is divided into first and second hydrocarbon feeds, of which the first is subjected to catalytic partial oxidation and the second to steam reforming.
  • hydrocarbon containing feed suitable for steam reforming can be used.
  • the feed contains light hydrocarbons such as C1-4 alkanes, e.g. methane, ethane, etc. More preferably, the feed contains methane or a gas containing substantial amounts of methane, e.g. natural gas. It is preferred to use a desulfurized feed. Therefore, if needed, the hydrocarbon feed can be subjected to a desulfurization step prior to dividing into two feeds. Under hydrocarbon feed any feed containing at least one hydrocarbon is meant.
  • the ratio of dividing the feed into two feeds is dependent on the feed composition and on a desired composition of the final synthesis gas.
  • the desired composition is determined by the final application of the synthesis gas, e.g. methanol production in a particular case.
  • the second synthesis gas e.g. methanol production in a particular case.
  • hydrocarbon feed which will be supplied to a steam reformer, constitutes preferably less than a half of the whole hydrocarbon feed in volume, and preferably 5 to 30 vol.% of the total hydrocarbon containing feed is divided as the second hydrocarbon feed.
  • the volume ratio of the first hydrocarbon feed to the second hydrocarbon feed is preferably from 20: 1 to 2: 1, and more preferably from 15: 1 to 5: 1.
  • the second feed is preferably 5-15 vol.% of the whole hydrocarbon feed. Best results are achieved when the second feed is about 10 vol.% of the whole hydrocarbon feed.
  • the hydrocarbon feed, or part of it can be subjected to pre- reforming.
  • the first hydrocarbon feed is subjected to catalytic partial oxidation (CPO).
  • CPO catalytic partial oxidation
  • This typically involves a reaction of hydrocarbons with steam and oxygen in the presence of a catalyst.
  • the reaction can be represented as follows:
  • the R ratio of the product is typically 1.87.
  • the reaction is typically performed at a temperature of 800-900°C in the presence of a metal catalyst.
  • the catalytic metal is preferably a Group VIII noble metal, e.g., platinum, iridium, rhodium, osmium, ruthenium, although nickel may also be used as the catalytic metal.
  • the oxygen used in the catalytic partial oxidation process may be pure or substantially pure oxygen or an oxygen containing gas, e.g., air, or a mixture of oxygen with an inert gas. Substantially pure oxygen (that is, containing more than 99% oxygen) is preferred, and pure oxygen containing more than 99.9% oxygen is still more preferred.
  • the feed stream supplied to the CPO reactor is preferably preheated to a temperature of 200-500°C, preferably 350-450°C and in particular about 400°C. At these temperatures, the supply of oxygen to the CPO reactor is minimized. This also reduces the costs for the air separation unit (ASU), in case the latter is used to obtain oxygen for the CPO reaction. Preheating can conveniently be done in a convection section of a steam reformer.
  • the hydrocarbon containing feed and the oxygen can be in various ratios in the feed gas mixture. The precise mixture introduced into the reaction zone depends on the particular hydrocarbons used and the amount of oxygen necessary to conduct the partial oxidation reaction. Operable ratios can be easily determined by one skilled in the art. Usually, the O2/C (Oxygen to Carbon) ratio is around 0.4 - 0.6, preferably 0.5.
  • CPO also referred to as SCT-CPO
  • SCT-CPO refers to Short Contact Time Catalytic Partial Oxidation.
  • the CPO reaction takes place in a reactor under the influence of a catalyst at residence times between 10" 2 to 10" 4 and with typical catalyst surface contact times around 10" 6 S " 1 . These contact time correspond to typical space velocities of 100,000 to 250,000 hr 1 , preferably 100,000 to 200,000 hr 1 .
  • Catalysts employed for SCT-CPO comprise Ni, Pd, Pt, Rh, or Ru.
  • the reaction takes place at catalyst surface temperatures above 950°C, preferably above 1000°C.
  • a reference to CPO is (a) L. Basini, Catalysis Today 117 (2006) 384-393. Other references include (b) L. Basini, K. Aasberg-Petersen, A. Guarinoni, M.
  • a first reaction product mixture comprising hydrogen (H2), carbon monoxide (CO) and carbon dioxide (CO2).
  • this reaction product mixture contains less carbon dioxide than in a conventional CRT process. This is particularly advantageous in methanol plants, which require a CO2 content as low as possible.
  • the first reaction product mixture comprises less than 10% CO2 dry basis, more preferably less than 6% CO2 dry basis.
  • the low carbon dioxide content contributes to the optimized R ratio of the end product synthesis gas, which R ratio cannot be obtained with conventional POX or conventional CPO methods.
  • part of the CO is converted into C02 in the presence of steam in a water gas shift (WGS) reactor, reducing thereby the CO/CO2 ratio in the reaction product mixture preferably to a value from 3 to 10, more preferably to a value from 6 to 7.
  • WGS water gas shift
  • the CO/CO2 ratio may further be adjusted by modifying the amount of gas flowing through a by-pass around the WGS reactor, if desired.
  • the second hydrocarbon feed is subjected to steam reforming (SR) in a steam reformer.
  • SR steam reforming
  • the feed can be subjected to pre- reforming.
  • higher hydrocarbons higher than Ci
  • the conversion reaction in the pre-reformer is particularly effective when the feed is introduced into the pre-reformer at a temperature of 250-600°C, preferably 450-550°C and in particular about 500°C.
  • Preheating of the pre-reforming feed can conveniently be done in a convection section of the SR section.
  • An adiabatic steam reforming can be used as pre-reforming.
  • the steam-to-carbon molar ratio is preferably from 1.5 to 2, more preferably about 1.6 - 1.7.
  • the oxygen is treated in a pre- reforming, preferably in an adiabatic steam reforming, the oxygen
  • the steam reforming is preferably followed by a water gas shift reaction to convert CO to CO2 and additional 3 ⁇ 4.
  • the product mixture can also be purified to separate CO2 and obtain a hydrogen-rich stream.
  • the carbon dioxide is removed from the second reaction product mixture by pressure swing adsorption (PSA).
  • PSA pressure swing adsorption
  • the second reaction product mixture is then combined with the first reaction product mixture. In this way, the R ratio is raised to above 1.9, and preferably to about 2.
  • the duty of a steam reforming section can be reduced to a value between 30 to 70% and preferably 40-50% of that in the conventional Combined Reforming.
  • the CO2 emissions are reduced at least by 50% compared with the conventional technology.
  • the present invention provides a method to operate the steam reformer more efficiently in a process for making synthesis gas for making methanol.
  • very large steam reformer units are needed which requires a very costly investment.
  • these units are typically operated with an excess of hydrogen.
  • the present invention leads to an optimized process with a high yield of methanol with the minimum energy usage in steam reforming.
  • Another advantage of the process is that typically the WGS reaction and the CO2 removal, e.g. by PSA, only need to be applied to the second reaction mixture.
  • the resulting synthesis gas has the R ratio, being molar ratio (3 ⁇ 4 - CO2) / (CO + CO2), that is particularly suitable for methanol production.
  • the R ratio is in the range of 1.90-2.20, more preferably 1.95-2.05.
  • parameter R is defined such that the R ratio does not change during the WGS step.
  • CO is converted into CO2 with formation of H2, but the R ratio stays the same. This can be explained by that in the WGS reaction for every mole of CO that is converted to CO2 one mole of 3 ⁇ 4 is produced.
  • the difference (H2-CO2) thus stays the same as well as the sum (CO+CO2).
  • the R ratio is thus only influenced by the mixing of the first and second reaction mixture.
  • the present invention relates to a method for producing methanol from a hydrocarbon containing feed.
  • the method comprises the steps previously described to obtain a synthesis gas, which synthesis gas is then used to produce methanol. Any suitable method to produce methanol from synthesis gas can be used.
  • carbon oxides and hydrogen from the synthesis gas react on a catalyst to produce methanol.
  • the catalyst for this reaction usually contains copper and zinc.
  • the present invention relates to a method for adapting an existing methanol plant comprising a steam reforming unit to the methanol production process according to the present invention, said method comprising adding a CPO unit in parallel with the steam reforming unit, to the existing methanol plant.
  • CPO unit also SCT-CPO units are meant, as described above.
  • the steam reforming unit preferably comprises a steam reformer and a shift reactor for performing the water-gas shift reaction.
  • the CPO unit is installed in an existing methanol plant in such a way that makes it possible to conduct the methanol production process as described above.
  • the CPO unit is installed in parallel with the SR unit, which in turn may comprise a steam reformer and a shift (WGS) reactor.
  • FIG. 1 illustrates a known combined technology process.
  • a natural gas feed 100 is desulfurized in a hydrodesulfurization (HDS) reactor 1.
  • a desulfurized feed 120 is then subjected to pre-heating in a convection section 50 of a steam reformer (SR).
  • SR steam reformer
  • Preheated stream 121 is added with steam and is further supplied to a pre-reformer 11, whereafter the stream is split into two streams, 122 and 123.
  • Stream 122 is supplied to the steam reformer 5, in which natural gas together with steam is catalytically converted to a synthesis gas 124.
  • Stream 123 is mixed with synthesis gas 124 and both are fed into an autothermal reformer (ATR) 2.
  • ATR autothermal reformer
  • the mixed gas stream together with oxygen is reformed to a synthesis gas 106, which has a proper composition to be used (after compression) for methanol synthesis in a synthesis reactor 6.
  • a hydrocarbon feed 100 is desulfurized in a HDS reactor 1.
  • the feed stream is preheated in a convection section 50 of a steam reformer, and then split in two streams, 101 and 102.
  • Stream 101 is added with steam, subjected to pre-reforming in a pre-reforming section 11 and then supplied to a SR section, which contains a SR reactor 5 together with a HT shift reactor 51, followed by a pressure-swing adsorption (PSA) unit 53.
  • PSA pressure-swing adsorption
  • CO2 can be removed in unit 52 preceding (or replacing) the PSA unit 53; CO2 removal is obtained through a solvent wash system, such as amine, selexol or other known solvents. After PSA, a pure 3 ⁇ 4 stream 110 is obtained.
  • a solvent wash system such as amine, selexol or other known solvents.
  • Stream 102 together with a super heated steam is mixed with preheated oxygen and enters the catalyst bed of the CPO reactor 2.
  • the produced gas 103 cooled in a process gas boiler 3 to yield stream 104, which is split thereafter into two streams, one of which is introduced into a CO shift reactor 4 and the other by-passes it. Before being introduced into the CO shift reactor, further steam is added to the first stream.
  • the streams are
  • stream 105 which stream is characterized by the same R ratio as stream 103 but has a decreased CO/CO2 ratio, which is aligned to about 2.6.
  • Streams 105 and 110 are mixed to obtain stream 106 which is supplied, after compression, to a methanol synthesis reactor 5.
  • the ratio H2/CO of stream 106 is about 3 and the R ratio is about 2.
  • the ratio of splitting of the feed into streams 101 and 102 depends on the feed composition and H2/CO ratio.
  • the R is 2 and the H2/CO ratio is about 3: 1.
  • feed stream 101 constitutes preferably about 5-30 vol.% of stream 100. If natural gas is applied, this stream is preferably less than 10% of the entire feed stream 100. In other applications, however, up to 30% of the feed can be branched off as stream 101.
  • FIG 3 shows another preferred embodiment of the present invention.
  • a feed stream 120 is obtained which is heated in a convection section 50 of a reformer to about 500°C and is supplied to a pre-reformer 11. Downstream of the pre-reformer 11, the stream is split into two streams, supplied to CPO and SR sections.
  • the remaining part of this scheme corresponds to that of Figure 2, so that reference can be made to the above explanations. Accordingly, identical components of the plant are provided with the same reference numerals.
  • heavy natural gas is processed using heat provided by the convection section 50 of the SR, which leads to the reduction of oxygen consumption and the reduction of the overall size of the SR section.
  • the WGS ratio is the ratio between the stream sent to the shift reactor and the total effluent from the CPO.
  • Case 1 is an embodiment according to the present invention, wherein pre-reforming of steam reforming feed and no recycling of a product purge gas from PSA to the CPO reactor are performed.
  • Case 2 is an embodiment according to the present invention, wherein pre-reforming of steam reforming feed and recycling about 50% of product purge gas from PSA to the CPO reactor are performed.
  • Case 3 is an embodiment according to the present invention, wherein pre-reforming of steam reforming feed and pre-reforming of 40% of CPO feed are performed
  • Case 4 is similar to case 1 but has a steam-to-carbon molar ratio of 0.4 of the feed supplied to the CPO reactor.
  • the steam-to-carbon molar ratio of a feed supplied to the pre-reformer is 1.5, while the steam-to-carbon molar ratio supplied to the steam reformer is 3.
  • Table 1 demonstrates the reduction of feed and fuel consumption and of the reformer duty for several embodiments of the present invention compared to a known combined reforming technology.
  • the reduction of the reformer duty translates, in turn, into a considerable reduction of the capital costs of the plant and reduced CO2 emission.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé de production de syngaz à partir d'une charge contenant des hydrocarbures, ledit syngaz étant particulièrement adapté à une utilisation subséquente dans la production de méthanol. Selon ce procédé, une charge (100) est divisée en deux flux, un flux étant soumis à une oxydation catalytique partielle (CPO) (2) et l'autre flux étant soumis au vaporeformage (5) puis à une réaction de conversion du gaz à l'eau (51). Les deux flux sont ensuite réassociés et peuvent servir ultérieurement à la synthèse de méthanol (6). Le flux réassocié présente de préférence un rapport R, à savoir un rapport molaire (H2-C02)/(CO+C02), compris entre 1,9 et 2,2, de préférence d'environ 2. L'invention concerne en outre un procédé de production de méthanol à partir d'une charge contenant des hydrocarbures, le premier syngaz étant obtenu selon le procédé de l'invention, lequel syngaz est utilisé ultérieurement pour la production de méthanol. L'invention porte également sur un procédé pour adapter une usine de production de méthanol existante au procédé de production de méthanol de l'invention.
PCT/NL2012/050748 2011-10-26 2012-10-26 Procédé de production de syngaz pour la production de méthanol WO2013062415A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN201280053004.5A CN103889891B (zh) 2011-10-26 2012-10-26 生产用于生产甲醇的合成气的方法
DK12783359.8T DK2771275T3 (da) 2011-10-26 2012-10-26 Fremgangsmåde til fremstilling af syntesegas til methanolfremstilling
EP12783359.8A EP2771275B1 (fr) 2011-10-26 2012-10-26 Procédé de production de gaz synthétique pour la production de méthanol
EA201400498A EA026825B1 (ru) 2011-10-26 2012-10-26 Способ получения синтез-газа для производства метанола
US14/354,536 US9102532B2 (en) 2011-10-26 2012-10-26 Method for producing synthesis gas for methanol production
CA2853421A CA2853421C (fr) 2011-10-26 2012-10-26 Procede de production de syngaz pour la production de methanol

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11186764.4 2011-10-26
EP11186764 2011-10-26

Publications (1)

Publication Number Publication Date
WO2013062415A1 true WO2013062415A1 (fr) 2013-05-02

Family

ID=47144031

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2012/050748 WO2013062415A1 (fr) 2011-10-26 2012-10-26 Procédé de production de syngaz pour la production de méthanol

Country Status (7)

Country Link
US (1) US9102532B2 (fr)
EP (1) EP2771275B1 (fr)
CN (1) CN103889891B (fr)
CA (1) CA2853421C (fr)
DK (1) DK2771275T3 (fr)
EA (1) EA026825B1 (fr)
WO (1) WO2013062415A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016016253A1 (fr) * 2014-07-29 2016-02-04 Eni S.P.A. Procédé intégré de reformage par oxydation catalytique partielle/chauffé au gaz à temps de contact court pour la production de gaz de synthèse
WO2022235334A1 (fr) * 2021-05-03 2022-11-10 Utility Global, Inc. Système de production d'hydrogène et procédé d'utilisation

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016083434A1 (fr) * 2014-11-25 2016-06-02 Haldor Topsøe A/S Procédé de génération de gaz de synthèse par recyclage de gaz de combustion
ES2970247T3 (es) * 2018-09-19 2024-05-27 Eni S P A Procesos para la producción de metanol a partir de hidrocarburos gaseosos
WO2020142489A1 (fr) * 2019-01-02 2020-07-09 Sabic Global Technologies, B.V. Enrichissement en hydrogène dans un gaz de synthèse produit par oxydation catalytique partielle
EA202191930A1 (ru) * 2019-01-17 2021-09-28 Эни С.П.А. Способ производства метанола из синтез-газа, произведенного каталитическим частичным окислением, интегрированным с крекингом
AU2020208782A1 (en) * 2019-01-18 2021-06-10 Haldor Topsøe A/S Method for the preparation of methanol synthesis gas
EA202191918A1 (ru) * 2019-01-21 2021-10-18 Эни С.П.А. Способ производства метанола
EP3921280A1 (fr) * 2019-02-06 2021-12-15 ENI S.p.A. Procédé de production de méthanol avec efficacité énergétique accrue
US11578016B1 (en) 2021-08-12 2023-02-14 Saudi Arabian Oil Company Olefin production via dry reforming and olefin synthesis in a vessel
US11718575B2 (en) 2021-08-12 2023-08-08 Saudi Arabian Oil Company Methanol production via dry reforming and methanol synthesis in a vessel
US11787759B2 (en) 2021-08-12 2023-10-17 Saudi Arabian Oil Company Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel
US11617981B1 (en) 2022-01-03 2023-04-04 Saudi Arabian Oil Company Method for capturing CO2 with assisted vapor compression

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0233076A2 (fr) 1986-02-10 1987-08-19 Foster Wheeler Energy Limited Procédé de production de gaz de synthèse
US5252609A (en) * 1991-07-09 1993-10-12 Imperial Chemical Industries Plc Synthesis gas production
EP0640559A1 (fr) 1993-08-27 1995-03-01 SNAMPROGETTI S.p.A. Procédé pour l'oxydation partielle de gaz naturel pour obtenir le gaz de synthèse et le formaldehyde
WO1997037929A1 (fr) 1996-04-11 1997-10-16 Snamprogetti S.P.A. Materiel destine a des reactions d'oxydation partielle
WO2000000426A1 (fr) 1998-06-30 2000-01-06 Shell Internationale Research Maatschappij B.V. Oxydation catalytique partielle via un catalyseur a alliage rhodium-iridium
WO2001032556A1 (fr) 1999-10-29 2001-05-10 Exxon Research And Engineering Company Procede d'oxydation catalytique partielle utilisant des catalyseurs sous forme de particules
WO2001036323A2 (fr) 1999-11-17 2001-05-25 Conoco Inc. Catalyseurs a base de cobalt et procede de production de gaz de synthese
EP1219566A1 (fr) * 2000-12-27 2002-07-03 L'air Liquide, S.A. à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude Procédé et dispositif intégré pour la production de gaz de synthèse
WO2006117499A1 (fr) * 2005-05-03 2006-11-09 Quartey-Papafio Alexander H Procede de fabrication d'un gaz de synthese
US20080275143A1 (en) * 2003-03-16 2008-11-06 Kellogg Brown & Root Llc Catalytic Partial Oxidation Reforming for Syngas Processing and Products Made Therefrom
EP2199254A1 (fr) * 2008-12-11 2010-06-23 BP p.l.c. Raffinerie de gaz intégré
WO2011072877A1 (fr) * 2009-12-16 2011-06-23 Eni S.P.A. Procédé de production d'hydrogène à partir d'hydrocarbures liquides, gazeux et/ou de composés oxygénés également issus de biomasses

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040171701A1 (en) * 2001-11-02 2004-09-02 Technology Convergence Inc. Methanol production process
US6797252B2 (en) * 2002-11-25 2004-09-28 Conocophillips Company Hydrocarbon gas to liquid conversion process
US7485767B2 (en) * 2005-06-29 2009-02-03 Exxonmobil Chemical Patents Inc. Production of synthesis gas blends for conversion to methanol or Fischer-Tropsch liquids
DK2464598T3 (da) * 2009-08-14 2013-10-28 Saudi Basic Ind Corp Kombineret reformeringsproces til methanolproduktion

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0233076A2 (fr) 1986-02-10 1987-08-19 Foster Wheeler Energy Limited Procédé de production de gaz de synthèse
US5252609A (en) * 1991-07-09 1993-10-12 Imperial Chemical Industries Plc Synthesis gas production
EP0640559A1 (fr) 1993-08-27 1995-03-01 SNAMPROGETTI S.p.A. Procédé pour l'oxydation partielle de gaz naturel pour obtenir le gaz de synthèse et le formaldehyde
WO1997037929A1 (fr) 1996-04-11 1997-10-16 Snamprogetti S.P.A. Materiel destine a des reactions d'oxydation partielle
WO2000000426A1 (fr) 1998-06-30 2000-01-06 Shell Internationale Research Maatschappij B.V. Oxydation catalytique partielle via un catalyseur a alliage rhodium-iridium
WO2001032556A1 (fr) 1999-10-29 2001-05-10 Exxon Research And Engineering Company Procede d'oxydation catalytique partielle utilisant des catalyseurs sous forme de particules
WO2001036323A2 (fr) 1999-11-17 2001-05-25 Conoco Inc. Catalyseurs a base de cobalt et procede de production de gaz de synthese
EP1219566A1 (fr) * 2000-12-27 2002-07-03 L'air Liquide, S.A. à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude Procédé et dispositif intégré pour la production de gaz de synthèse
US20080275143A1 (en) * 2003-03-16 2008-11-06 Kellogg Brown & Root Llc Catalytic Partial Oxidation Reforming for Syngas Processing and Products Made Therefrom
WO2006117499A1 (fr) * 2005-05-03 2006-11-09 Quartey-Papafio Alexander H Procede de fabrication d'un gaz de synthese
EP2199254A1 (fr) * 2008-12-11 2010-06-23 BP p.l.c. Raffinerie de gaz intégré
WO2011072877A1 (fr) * 2009-12-16 2011-06-23 Eni S.P.A. Procédé de production d'hydrogène à partir d'hydrocarbures liquides, gazeux et/ou de composés oxygénés également issus de biomasses

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"Ullmann's Encyclopedia of Industrial Chemistry", 15 October 2011, WILEY-VCH VERLAG GMBH & CO. KGAA, Weinheim, Germany, ISBN: 978-3-52-730673-2, article RAINER REIMERT ET AL: "Gas Production, 5. Examples of Complex Gas Production Plants", XP055049320, DOI: 10.1002/14356007.o12_o04 *
BASINI ET AL: "Fuel rich catalytic combustion: Principles and technological developments in short contact time (SCT) catalytic processes", CATALYSIS TODAY, ELSEVIER, NL, vol. 117, no. 4, 15 October 2006 (2006-10-15), pages 384 - 393, XP027976254, ISSN: 0920-5861, [retrieved on 20061015] *
D. HICHMAN; L.D. SCHMIDT, SCIENCE, vol. 259, 1993, pages 343
H. HICKMAN; L.D. SCHMIDT, J. CATAL., vol. 138, 1992, pages 267
L. BASINI, CATALYSIS TODAY, vol. 117, 2006, pages 384 - 393
L. BASINI; K. AASBERG-PETERSEN; A. GUARINONI; M. OESTBERG: "Catalytic Partial Oxidation of Natural Gas at Elevated Pressure and Low Residence Time", CATALYSIS TODAY, vol. 64, 2001, pages 9 - 20

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016016253A1 (fr) * 2014-07-29 2016-02-04 Eni S.P.A. Procédé intégré de reformage par oxydation catalytique partielle/chauffé au gaz à temps de contact court pour la production de gaz de synthèse
WO2022235334A1 (fr) * 2021-05-03 2022-11-10 Utility Global, Inc. Système de production d'hydrogène et procédé d'utilisation
US11879179B2 (en) 2021-05-03 2024-01-23 Utility Global, Inc. Hydrogen production system and method of use

Also Published As

Publication number Publication date
US20150087865A1 (en) 2015-03-26
CA2853421C (fr) 2019-04-23
CN103889891A (zh) 2014-06-25
EA201400498A1 (ru) 2014-09-30
EP2771275A1 (fr) 2014-09-03
DK2771275T3 (da) 2019-08-19
CA2853421A1 (fr) 2013-05-02
US9102532B2 (en) 2015-08-11
EA026825B1 (ru) 2017-05-31
CN103889891B (zh) 2016-09-14
EP2771275B1 (fr) 2019-07-24

Similar Documents

Publication Publication Date Title
US9394219B2 (en) Method for producing synthesis gas for methanol production
US9102532B2 (en) Method for producing synthesis gas for methanol production
US9067850B2 (en) Synthesis gas and Fischer Tropsch integrated process
CN107021450B (zh) 用于制备氨和尿素的方法
EP2994415B1 (fr) Procédé de production d'un gaz de synthèse à base d'ammoniac avec une conversion à température élevée et un rapport vapeur/carbone faible
KR20200031646A (ko) 합성 가스의 제조 방법
AU2003232578B2 (en) Integrated process for making acetic acid and methanol
EA030740B1 (ru) Способ для производства богатых водородом газовых смесей
WO2013013895A1 (fr) Procédé de production de gaz de synthèse
AU2010241012A1 (en) Production of a synthesis gas blend and use in a Fischer-Tropsch process
CA3126620A1 (fr) Installation de synthese de produit chimique et methode d'utilisation du dioxyde de carbone
EP3362405B1 (fr) Procédé de production et unité de production de méthanol
AU2002317859B2 (en) Integrated process for hydrocarbon synthesis
AU2002317859A1 (en) Integrated process for hydrocarbon synthesis

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12783359

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2853421

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 14354536

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2012783359

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 201400498

Country of ref document: EA